Abstract
The isotherms of absolute methane adsorption in an Fe–BDC metal–organic porous structure after long-term storage were measured at a pressure as high as 40 MPa and the temperatures of 303, 313, 323, and 333 K. The dependences of differential molar isosteric heats of adsorption and entropies of adsorption on methane uptake were calculated. It was shown that taking into account the nonideality of a gaseous phase and steepness of the isotherm of adsorption leads to a temperature dependence of thermodynamic functions of adsorption. Both a sharp drop in the heat of adsorption and a local maximum of the entropy at the maximum values of methane uptake are indicative of rearranging the adsorbate structure and the probable formation of molecular methane associates in micropores.
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REFERENCES
Dubinin, M.M., Adsorbtsiya i poristost' (Adsorption and Porosity), Moscow: Military Academy of Chemical Defense Named after Marshal of the USSR S.K. Timoshenko, 1972.
Tsivadze, A.Yu., Aksyutin, O.E., Ishkov, A.G., Knyazeva, M.K., Solovtsova, O.V., Menshchikov, I.E., Fomkin, A.A., Shkolin, A.V., Khozina, E.V., and Grachev, V.A., Russ. Chem. Rev., 2019, vol. 88, no. 9, p. 925.
Knyazeva, M.K., Tsivadze, A.Yu., Solovtsova, O.V., Fomkin, A.A., Pribylov, A.A., Shkolin, A.V., Pulin, A.L., and Men’shchikov, I.E., Prot. Met. Phys. Chem. Surf., 2019, vol. 55, no. 1, p. 9.
Batrakova, M.K., Solovtsova, O.V., Fomkin, A.A., Tsivadze, A.Yu., Shkolin, A.V., Shiryaev, A.A., and Vysotskii, V.V., Prot. Met. Phys. Chem. Surf., 2017, vol. 53, no. 6, p. 961.
Cychosz, K.A. and Matzger, A.J., Langmuir, 2010, vol. 26, p. 17198.
Qadir, N.U., Said, S.A.M., and Bahaidarah, H.M., Microporous Mesoporous Mater., 2015, vol. 201, no. 1, p. 61.
Knyazeva, M.K., Shkolin, A.V., Fomkin, A.A., Tsivadze, A.Yu., Solovtsova, O.V., Platonova, N.P., Pulin, A.L., Men’shchikov, I.E., Shiryaev, A.A., Vysotskii, V.V., and Kiselev, M.R., Prot. Met. Phys. Chem. Surf., 2018, vol. 54, no. 6, p. 1004.
Sychev, V.V., Vasserman, A.A., Zagoruchenko, V.A., Kozlov, A.D., Spiridonov, G.A., and Tsymarnyi, V.A., Termodinamicheskie svoistva metana (Thermodynamic Properties of Methane), Moscow: Izd. Standartov, 1979.
Pribylov, A.A., Kalashnikov, S.M., and Serpinskii, V.V., Izv. Akad. Nauk SSSR, Ser. Khim., 1990, no. 6, p. 1233.
Shen, D. and Bulow, M., Microporous Mesoporous Mater., 1998, vol. 22, p. 237.
Shkolin, A.V., Fomkin, A.A., and Sinitsyn, V.A., Colloid J., 2008, vol. 70, no. 6, p. 796.
Fomkin, A.A., Men’shchikov, I.E., Pribylov, A.A., Gur’yanov, V.V., Shkolin, A.V., Zaitsev, D.S., and Tvardovskii, A.V., Colloid J., 2017, vol. 79, no. 1, p. 144.
Shkolin, A.V., Fomkin, A.A., Men’shchikov, I.E., Strizhenov, E.M., Pulin, A.L., and Khozina, E.V., Adsorption, 2019, vol. 25, no. 8, p. 1559.
Fomkin, A.A. and Shkolin, A.V., Dokl. Phys. Chem., 2008, vol. 423, no 1, p. 292.
Men’shchikov I.E., Shkolin A.V., Fomkin A.A. Measurement Techniques, Instrument Society of America (United States), 2017, vol. 60, no 10, p. 1051.
Shkolin, A.V., Fomkin, A.A., and Potapov, S.V., Russ. Chem. Bull., 2017, vol. 66, no. 4, p. 607.
https://trc.nist.gov/refprop/MINIREF/MINIREF.HTM.
Fomkin, A.A., Adsorption, 2005, vol. 11, nos. 3–4, p. 425.
Fomkin, A.A., Regent, N.I., and Serpinskii, V.V., Izv. Akad. Nauk SSSR, Ser. Khim., 1989, no. 9, p. 2137.
Funding
This work was carried out within the framework of a state order, project no. 01201353185, and a plan of the Scientific Council of the Russian Academy of Sciences in Physical Chemistry, heme no. 20-03-460–01.
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Translated by E. Khozina
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Knyazeva, M.K., Tsivadze, A.Y., Fomkin, A.A. et al. Methane Adsorption on Fе–BDC Metal–Organic Porous Structures at High Pressures. Prot Met Phys Chem Surf 56, 682–687 (2020). https://doi.org/10.1134/S2070205120040152
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DOI: https://doi.org/10.1134/S2070205120040152